The TiCl4 or SnCl4 mediatedDiels-Alderreaction of cyclopentadiene and chiral acryloyl ester derivedfromchiral cyclitols proceeded with excellent diastereoselectivity in Et2O via re-face attack of the acrylates. In contrast, interesting changeover of the diastereofacial selectivity was observed by use of toluene or hexane as a solvent to afford the cycloadducts derivedfrom si-face attack of the